Metallo-organic compound and method of preparing the same



T v UNITED STATE agents as starting Accordingly, an object oiltheinventionls to memes May 30, 1944 S PAT'ENT. OFFICE METALLO-ORGANICCOMPOUND AND METHOD F PREPABING THE SAME George B. Denison, Jr.,Berkeley, and Arthur C. Ettling, Richmond, CaliL, assignors to Stand ardOil Company of California, San Francisco, Calit. a corporation ofDelaware No Drawing. Application May 21, 1940,

- Serial N0. 836,392

11 Claims. (61.26MB?) This invention relates to methods of preparingmetal compounds of organic acids and involves,

as a preferred group, the preparation of metal salts of high molecularweight organic acids.

Methods utilized heretofore in the preparation of metal salts of highmolecular weight organic acids have involved various difliculties. Thisis particularly true where metal salts of relatively weak bases, such asthe alkaline earth metals and/or high molecular weight water-insolubleorganic acids, are involved Often expensive raw materials have beenrequired and extended purification methods were necessary to obtain theproduct of the desired purity and characteristics. For example, whensalts of high molecular weight water-insoluble organic acids areprepared by double decomposition in the presence of an aqueous medium,various undesirable reaction products'are sometimes separable only afterextended washing or other purification steps.

Additional dimculties have been encountered where the metallic compoundof the high molecular weight organic acids is amorphous or has a highmelting point. Ithas been found, for

,instance, that when water is present during preparation of suchcompounds, the salts tend to hold the water so intimately that it can besubsequently removed only by heating to such high temperatures as willpartially decompose or-deteriorate the compound. The water formed byreaction of an hydroxide with an acidic hydro gen, as in some priorproposed methods of preparation, is found to introduce this diificultyand materially alter the solubility of the saltin organic solvent suchas petroleum hydrocarbons. The

amount of water necessary to materially alter the solubility or otherproperties of these compounds is, in some instances, quite small.

provide an improved-method elf preparing metal compounds-of organicacids.

- 'Another-ob-ject oi the invention is to produce metal salts of highmolecular weight organic acids by an improved process which gives ahighyield of a product that is relatively free from inorganic salts andaqueous contaminations.

A further object is to provide a process which enables one to readilyproduce metal salts of very components in addition-to carbon, hydrogenand oxygen present in all organic acids.v The term high molecular weightorganic acids is intended to designate acids having a .molecular weightmore than approximately 100.

Example of acids which are to be regarded as organic acids within themeaning of this term, as herein u'sed, andwhich fall within the broadscope of the present invention comprise substituted acids of phosphoruscontaining an organic substituent, substituted sulfuric acids,

We have discovered that metal compounds 01 organic acids can beadvantageously prepared by reacting, in a non-aqueous environment, acarbide of a metal and the organic acid. This process is particularlyadvantageous when applied to high molecular weight orhani Despit thefact that the high molecular weight organic acids are extremely weak andin general relatively unreactive, their metal saltshave been obtained inan anhydrous and relatively pure condition. High yields of the desiredcompounds have been obtained by using relatively cheap raw materialswhere other processes either gave a less desirable product or requiredmore expensive rematerials.

c acids.'

substituted acids of arsenic, phenols, sulionic acids, carbocycliccarboxylic acids, and aliphatic carboxylic acids. Phenolic, compoundsare acidic and are within the scope of the, invention, as willbeapparent from the remaining disclosure.

' The following comprise examples of substituted acids of phosphoruswhich may be used in the present process:

O n-o-i -on o Mouoeeteroiorthophosphorlcscid mm oi ortbophospborio acidR-P 4 on i Phosphcnomaoid Mono-ester of phosphonous acid P-OHPhosphlnous acid OH RP Phosphonic acid O O R ,Mono-ester of phosphonicacid POH R ii Phosphinlc acid In the above formulae, R may b alkyl,aryl, alkaryl, aralkyl or cyclic non-benzenoid groups.

Similarly, a corresponding series of substituted sulfurous or sulfuricacids or partially esterified sulfur-containing acids, such as sulfuricacid, are

contemplated as falling within the broad scope oi taining organic groupsof alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid types.

Additional examples of organic acids comprise carboxylic acidscontaining carbocyclic nuclei, e. g. aryl, alkaryl, aralkyl or cyclicnon-benzenoid types. Examples of such acids comprise phenyl stearicacid, naphthenic acids, naphthoic acids, benzoic acid, and the like. Theprocess is also applicable to high molecular weight aliphatic acids,such as stearic, palmitic, myristic, lauric and oleic acids.

The process of the invention is particularly suited for and finds a mostuseful application in the preparation of metal salts of water-insolublephenols. Specific examples of suitable water-insoluble phenols comprisethe alkyl phenols such as p-octyl phenol, p-lauryl (dodecyl) phenol andp-cetyl phenol.

It is understood that the process is applicable to the preparation ofmetal salts of other high p it is intended to designate acids conclaimsto designate, generically, phenols which T5- are characterized by anacid group comprising one or more OH radicals directly attached to anaromatic nucleus. These phenols or phenolic compounds are representedgenerically by the.

type formula:

in which M is a metal; 12, w, x, y and z are selected from the groupconsisting of hydrogen, hydrocarbon, oxy and hydroxyl radicals; n is thevalence of the metal;' and in which the phenolic radical preferably hasan alkyl group containing more than four carbon atoms. The hydrocarbo 1group above mentioned may be an alkyl, aryl, alkaryl, aralkyl or cyclicnon-benzenoid group. By the term oxy radical hereinabove mentioned, itis intended to designate an hydroxyl group in which the hydrogen hasbeen replaced by sterification, etherification, neutralization or thelike.

As a specific example of a. phenol useful in the present process and amethod of preparing the same, the following is given:

Phenol and a butene polymer, having an apparent molecular weight of 194and obtained by polymerization of a mixture of butenes containingbutene-1, butene-2, and isobutene, were mixed. To this mixture,containing 237 grams of phenol and 500 grams of the above-mentionedbutene polymers, 140 cubic centimeters of 94%.sulfuric acid was addedslowly with agitation. The temperature was kept below 65 F. duringaddition of the acid. The mixture was agitated for twohours after theaddition of acid was completed and permitted to come to roomtemperature. The reaction product was then diluted with an equal volumof water and placed in a sealed autoclave where it was heated at 350 F.for an hour withagltation. The product was washed with water, 5% sodiumcarbonate solution and again with water in order to free it of sulfuricacid, sulfonates and unreacted phenol. A 93% yield of high molecularweight water-insoluble alkyl phenol having an acetyl number of '181 wasobtained.

A second example of a method of preparing an alky1 phenol is as follows:

511 grams of crude cresylic acid, 900 grams of an olefin polymercontaining an average of 14 carbon atoms per molecule and 475 grams of98% sulfuric acid were utilized in preparing an alkyl cresol. Theingredients were mixed, the temperature controlled and the productwashed as in the previous example. The reaction product was vacuumdistilled at 10 millimeters and a 50 to cut separated. This portion ofthe distillate had a molecular weight of 291' and was used to preparethe calcium salt of the alkyl cresol described in the examplehereinafter.

The above methods of preparing the alkyl phenols suitable for thepurposes oi this invention are merely illustrative. For example, othercon .The presence of the acetic acid facilitates temperature control andgives a softer, easier-handied reaction product.

As has been previously indicated, metal salts of high molecular weightorganic acids can be advantageously prepared by directly reacting theacid with a carbide of a metal. Suitable metal carbides are those whichreact with water to form acetylene.

The following comprise illustrative examples of processes utilizing theprinciples of this invention for the preparation of monohydroxy phenols:

Example 1.247 grams of an alkylatedphenol having an apparent molecularweight of 247 were agitated for six hours at 500 F. with 64 grams ofpowdered calcium carbide. A gaseous reaction product containingacetylene was formed and removed. The product remaining in the reactionzone was a dark-colored brittle solid at room temperature and comprisedacalcium salt of the alkylated phenol. 94% of the theoretical yield ofcalcium alkyl phenate was obtained as shown by an analysis of a sampleof the reaction product freed from calcium carbide by filtration of itspetroleum ether solution.

Example .2.685 gramsof an alkylated phenol having an apparent molecularweight of 290 were agitated for six hours at from approximately 500 F.to 540 F. with 90 grams of calcium carbide. A gas containing acetylenewas formed and removed. The product remaining in the reaction zone was adark-colored brittle solid at room temperature. A yield of calcium alkylphenate, representing 96% of that theoretically possible, was obtained.

The reactions occurring in the examples above disclosed may berepresented by the following equation:

. In the above equation, R represents an alkyl group but may be aryl,al'xaryl, aralkyl or cyclic non-benzenoid groups as heretoforeexplained. Likewise, the above react-ion is applicable to polyhydroxyphenols and to the preparation of phenates of polycyclic phenols inwhich the benzene ringsmay or may not be conjugated. The term "pheno orphenolic compounds is therefore used herein to designate genericallycompounds which contain one or more hydroxyl groups directly attached toan aromatic nucleus.

' Metal carbides other than calcium carbide give the above type reactionand may be utilized.

' analyzed as 9.5% calcium, and upon hydrolysis o! the salt 92% of thetheoretical amount of pphenol phenol was recovered.

Example of phenols containing coniugated benzene rings-A similarreaction to the above was carried out using beta naphthol and an excessof ground calcium carbide. The. product was only moderately soluble inchloroform or any other common solvent. A portion of the product wasextracted using chloroform and the solvent-free extract contained 10.5%calcium. Upon hydrolysis a 75% recovery of beta naphthol was obtained.

Example of a dihydroxy phenoL-Under conditions substantially the same asin the above, an excess of ground calcium carbide was reacted with4-p-tertiary butyl catechol. Evidence of reaction was as abovedescribed. The product was extracted with chloroform to give a brilliantindigo solution which when freed of solvent analyzed as 8.6% calcium,and upon .hydrolysis yielded roughly 80% of an organic substance whichave, upon distillation, of p-tertiary butyl catechol. The product of thereaction is believed to be Example of trihydroxy phenoL- Undersubstantially the same conditions as in all of the above, ground calciumcarbid and pyrogalloi were reacted. The some evidence of reaction wasnoted as in the other cases. The reaction product acne. This product wasthe calcium salt of the cyclohexyl phenol.

234 grams of an alkyl. cresol (molecular weight 291) and 25 grams ofpowdered calcium carbide Such other compounds comprise those metal car-.bldes which are known to react with water to yield acetylene. Thesemetal carbides are herein termed acetylides and comprise the carbides ofthe alkali metals and alkaline earth metals, namely sodium, potassium,rubidium, cesium, lithium, magnesium, calcium. strontium and berium. Toexemplify the reaction of these metal .carbides with phenolic compoundsgenerically,

were heated at 530 F. with stirring for four hours. The product is ahard brittle solid; soluble in mineral oil, and comprises a calcium saltof the alkyl cresol.

By way of further illustration, a metal salt of a substituted organicacid of phosphorus was prepared by reaction with a metal carbide asfollows:

Example 3.-To 267 grams of mono-cetyl phosphoric acid were added slowlyand with agitation grams of finely powdered calcium carbide. Thetemperature was held at 200 F. and the addition of the carbide carefullycontrolled to avoid excess tendency to foam. The total time forcompletion of the reaction was one hour.- The product was freed Ofexcess calcium carbide by dissolving in diethyl ether, filtering andevaporating oil the ether. Analysis for calcium showed com-. pleteconversion of the mono-cetyl phosphoric acid to calcium cetyl phosphate.

An example of the preparation of metal salts of carbocyclic carboxylicwater-insoluble organic acids is as follows:

Example 4.To 684 grams of naphthenic acid obtained from a Californiafuel oil fraction were added 75 grams of powdered calcium carbide. Themixture was heated in a flask with a-stirrer calcium naphthenateobtained was soluble in mineral oil in all proportions, and inconcentrations of 1 to 2% in oil did not materially increase theviscosity of the oil or cause gel formation. Calcium naphthenateprepared in an aqueous environment is soluble in oil in onlycomparatively small proportions and causes gel formation when added tolubricating oils in amounts as low as Any of th reactions hereindisclosed may be carried out in the presence of a non-aqueous, inertsolvent such as a hydrocarbon diluent like ously pointed outhereinbeiore. Certain of said high molecular weight'organic acids arewatersoluble." However, the invention finds a most useful field ofapplication in the preparation of metal salts of high molecular weightwater-insoluble organic acids, particularly th'oseof the carbocyclictype. The invention is especially useful with compounds of the phenolictype.

Thisapplication is a continuation-in-part of our parent applicationSerial No. 233,326, filed October 4, 1938, for Methods of preparingmetallo-organic compounds. Application Serial No. 233,327, filed October4, 1938, for Composition of matter and method of preparing the same, isdirected to the alkaline earth metal phenate species. While thecharacter of the invention has been described in detail, and numerousexamples of petroleum naphtha or mineral lubricating oil.

The presence of substantial quantities of water in the reaction zoneshould be avoided. The conditions under which the reaction is carriedout may be altered materially, depending upon. the time allowed for thereaction and upon the materials being reacted. Atmospheric pressure ispreferred but the invention'does not preclude the use of eithersub-atmospheric or superatmos-- may be intimately contacted with theorganic acid by agitation.

It has been observed that methyl alcohol tends to promote the reactionof calcium carbide with the high molecular weight alkyl phenols, andsuch an alcohol may be incorporated in the reaction zone.

The process of this invention has a number of advantages. It avoids theuse of an aqueous solvent as a medium for effecting the reactions and,as previously noted, thereby precludes difllculties often encountered byreason of impurities or bydrolysis of the reaction product. One couldnot predict that the high molecular weight waterinsoluble phenols,,suchas cetyl phenol, which are relatively stable and unreactive like hexylresorcinol, would react with calcium carbide and ,Ithe like innon-aqueous media. Another advantage of the process is that acetylenerather than water is formed by the reaction of the two initialcomponents and that this gas is easily removed without unduecontamination or modification of the tinished product. This lastfeatureis of particular utility in that the necessity for removingsubstantial amounts of reaction products comprising inorganic saltsand/or water is avoided. Other ad an environment substantially free ofwater.

weight greater than approximately 100, as previ- 76 the preparation andapplication of the process given; this has been done by way ofillustration only and with the intention that no limitation should beimposed upon the invention thereby. It will be apparent to those skilledin the art that numerous modifications and variations of theillustrative examples may be eiiected in the practice of the inventionwhich is of the scope of the claims appended hereto.

We claim:

1. A process of preparing metal salts of phenols which comprisesreacting an acetylide with a phenol in an environment substantially freeof water, whereby said metal salt is formed in the reaction zone. w

2. A process as in claim 2, in which the reaction is carried out in thepresence of an inert diluent.

3. A process as in claim 2, in which the reaction is carried out in thepresence of a hydrocarbon solvent. 4. A process as in claim 2, in whichthe reaction is carried out hol.

5. A process of preparing ametal compound of a phenol which comprisesdirectly reacting magnesium carbide with said phenol in an environmentsubstantially free of water,'whereby said metalcompound and a gaseousreaction product are formed.

6. A process of preparing a metal compound of a polyhydroxy phenol whichcomprises directly reacting an acetylide with a polyhydroxy phenol in anenvironment substantially free of water, whereby said metal compound anda gaseous reac ion product are formed.

'7. A process of preparing a metal compound of a polynuclear phenolwhich comprises directly reacting an acetylide with a polynuclear phenolin an environment substantially free of water, whereby said metalcompound and a gaseous reaction product are formed.

8. A process of preparing a metal compound of a water-insoluble phenolwhich comprises directly reacting an acetylide with said phenol in inthe presence of methyl alcowhereby said metal compound and a gaseousreact on product are formed. 9. A process of preparing a. metal compoundof a water-insoluble phenol which comprises directly reacting magnesiumcarbide with said phenol in an environment substantially free oi water,whereby said metal compound and a gaseous reaction product are formed.

10. A process of preparing a metal compound of an alkylated phenol whichcomprises directly reacting magnesium carbide with a water-insolublecarbon-alkyiated phenol in an environment substantially free of water,whereby said metal compound and a gaseous reaction product are formed.

11. A process of preparing a metal compound of a water-insoluble acidicorganic compound having a reactive hydrogen atom,which comprisesreacting an acetylide with said water-insoluble acidic compound in anenvironment substantially free of water to replace said reactivehydrogen with the metal of said acetylide and to form a gaseous reactionproduct comprising acetylene, and recovering the metal compound formedby said reaction.

GEORGE H. DENISON, JR.

ARTHUR C. E'ITLING.

CERTIFICATE OF CORRECTION. Patent No. 2, h9,79 May'fiO, 19m.

- GEORGE H. DENISON, JR., ET AL.

It is hereby, certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1;,sec- 0nd column, line 51+, claim 2, line 57, claim 5, and line k0,claimlp, for

the claim reference numeral "2" read -1--; and that the said LettersPetent should be read with this correction therein that the same mayconform to the record of the case in the Patent Office.

Signed and sealed this 25th day of July, A. D. 191m.

Leslie Frazer (Seal) Acting Commissioner of Patents.

